Chiral phosphines, valuable ligands for metal-catalyzed asymmetric reactions (Noyori Asymmetric Catalysis in Organic Synthesis; Wiley-Interscience: New York, 1994; Blaser and Schmidt, Eds. Asymmetric Catalysis on Industrial Scale. Challenges, Approaches, and Solutions; Wiley-VCH: Weinheim, 2004), are usually prepared either by resolution or by using a stoichiometric amount of a chiral auxiliary (Pietrusiewicz and Zablocka (1994) Chem. Rev. 94:1375-1411; Kagan and Sasaki, In: The Chemistry of Organophosphorus Compounds, F. R. Hartley, Ed., John Wiley and Sons: Chichester, England, 1990, Vol. 1, pp. 51-102). Metal-catalyzed asymmetric synthesis of these ligands has been carried out (Burk, et al. (1993) J. Am. Chem. Soc. 115:10125-10138; Hoge (2003) J. Am. Chem. Soc. 125:10219-10227; Shimizu, et al. (2003) Adv. Synth. Catal. 345:185-189; Marinetti and Genet (2003) C. R. Chimie 6:507-514. Enzymatic catalysis has also been employed: Shioji, et al. (2003) Tetrahedron Lett. 44:1103-1105; Kielbasinski, et al. (2003) Tetrahedron:Asymmetry 14:3379-3384; Kielbasinski, et al. (1994) Tetrahedron Lett. 35:7081-7084; Kagan, et al. (1994) Bioorg. Med. Chem. 2:15-21; Serreqi and Kazlauskas (1994) J. Org. Chem. 59:7609-7615 and P-stereogenic phosphines have been prepared via platinum-catalyzed hydrophosphination of activated alkenes (Kovacik, et al. (2000) Organometallics 19:950-953) and palladium-catalyzed phosphination of aryl halides (Moncarz, et al. (2002) J. Am. Chem. Soc. 124:13356-13357; Moncarz, et al. (2003) Organometallics 22:3205-3221; Korff and Helmchen (2005) Chem. Commun. 530-531; Pican and Gaumont (2005) Chem. Commun. 2393-2395).
Needed in the art is a catalytic process for preparing enantioenriched tertiary phosphines for use as ligands for homogeneous catalysis. The present invention meets this long felt need.